Dyeing human hair with 2-aminophenols

ABSTRACT

Hair dye compositions that contain a dye compound selected from the group consisting of 6-amino-4-methoxy-2-aminophenol, 5-amino4-methoxy-2-aminophenol, 6-amino-4-dimethylamino-2-aminophenol, 6-amino-4-diethylamino-2-aminophenol and 4-diethylamino-2aminophenol.

United States Patent 11 1 Kalopissis et a1.

DYEING HUMAN HAIR WITH v Z-AMINOPHENOLS Inventors: Gregoire Kalopissis, Paris; Andree Bugaut, Boulogne sur Seine, both of France Assignee: LOreal, Paris, France Filed: Aug. 31, 1970 Appl. No.: 68,488

Related US. Application Data Continnation-in-part of Ser. No. 645,521, June.12,

I967, abandoned, which is a continuation-in-part of Ser. No. 293,282, July 8, I963, abandoned.

US. Cl. 8/10.2, 8/11, 260/574,

- 260/575 1111. c1 A6lk 7/12 Field of Search 8/102, 11; 260/575 38,79 June 12, 1973 Primary Examiner-Albert T. Meyers Assistant ExaminerVera C, Clarke Attorney-Holcombe, Wetherill & Brisebois [57] ABSTRACT Hair dye compositions that contain a dye compound selected from the group consisting of 6-amino-4- methoxy-Z-aminophenol, 5-amino-4-methoxy-2- aminophenol, 6-amino-4-dimethylamino-2- aminophenol, 6-amino-4-diethylamino-2-aminophenol and 4-diethylamino-2-aminophenol.

9 Claims, No Drawings SUMMARY OF THE INVENTION commonly employed of these processes are those which use oxidation dyes whose coloration results from polymerization under oxidizing conditions.

In practice, the oxidation dyes employed are almost exclusively mixtures of aromatic diamines and aromatic aminophenols, generally known as bases, in

, combination with substances, generally called modifiers, such as substituted or unsubstituted monoand polyphenols. It is possible, by using a relatively limited number of aromatic bases and phenols, to obtain a fairly wide range of colorations, the proportions of the various constituents which enter into the composition of the dye bath being empirically varied. However, the formation of hair-coloring pigments from these mixtures results from a series of very complex chemical reactions which necessitate either the use of an oxidizing substance, almost exclusively hydrogen peroxide, or the presence of a substance having an alkaline reaction, which is generally ammonia. It is also known that by increasing the hydrogen peroxide and ammonia content there is obtained what is known as a decolorizing dye," there being simultaneously produced a decoloration of the hair to be dyed and a hair coloration in the desired shade.

It is well known that the hair-dyeing processes mentioned above have many disadvantages arising out of the mode of formation of the pigments imparting the coloration to the hair. In the first place, the use of paradiamines is likely to produce dermatitis and even allergies in certain particularly sensitive people. On the other hand, the necessary presence of alkali and of hydrogen peroxideleads to modifications of the structure of the hair, which may sometimes be undesirable. Moreover, the shades obtained by present techniques have a well known tendency to change in the course of time. Thus the colorations often tend to turn towards red; this is an appreciable disadvantage.

If, in this state of the art, that is to say, when an aromatic base and a modifier are used in combination, only known bases were to be employed, either alone or in admixture, products would be obtained which would have the aforesaid disadvantages in a higher degree and which, in addition, would give very limited ranges of shades.

According to the present invention it has now been discovered that it is possible to dye living hair without the use of the modifiers hitherto traditionally employed, provided that the aromatic bases heretofore employed are replaced by other selected products capable of developing a characteristic shade, which never varies, without the aid of an oxidizing or modifying agent. It has also been discovered that it is possible to use for this purpose solutions of these selected products having a slightly basic pH value, which may be as low as 7.

In this way, each of the selected bases employed develops its own shade. Consequently, an extensive range of commercially necessary shades may be made available merely by employing a number of these products, the final shade obtained being the component of the individual shades of the starting materials.

The present invention provides a new hair-dyeing .process which is essentially characterized by the fact that there is employed a dyeing solution containing at least one compound selected from the group consisting of 6-amino-4-methoxy-2-aminophenol, 5-amino-4- methoxy-Z-aminophenol, 6-amino-4-dimethylamino-2- aminophenol, 6-amino-4-diethylamino-Z-aminophenol and 4-diethylamino-2-aminophenol.

According to a feature of the invention, the dyeing solution comprises no oxidizing agent and no modifier and its pH value is equal to or higher than 7, viz. from 7 to 11, the necessary oxidation being induced by atmospheric oxygen.

According to a further feature of the invention, the dyeing solution contains, in addition to the aforesaid compound or compounds, hydrogen peroxide and an alkali, so as to effect a decolorizing dyeing effect. However, it still contains no modifier.

The process according-to the invention makes it possible to obtain greatly improved hair dyes by virtue of the fact that it is possible to use the coloring agents without a modifier, since each of the aforesaid bases develops its own shade as the result of a simple oxidation, and it is possible to obtain all the shades required in practice by simply mixing two or more of these bases.

According to a preferred method of carrying out the invention, the aforesaid compounds which are utilized for hair dyeing are stocked and brought into solution in the form of their salts, for instance in the form of their hydrochlorides or hydrobromides. When a base such as ammonia is also added to this solution, the compounds according to the invention are set free at the time of their utilization. Preferred hair dye compositions are aqueous solutions containing 0.5 to 5 percent by weight of the dye compound and which have a pH of 7 to 11.

In order that the invention may be more readily understood, there will now be described by way of illustration a number of embodiments.

EXAMPLE 1 Preparation of 2,6-diamino-4-methoxyphenol There is employed as starting material 2,6-dinitro-4- methoxyphenol, which is reduced in the usual way by means of a mixture of hydrochloric acid and tin.

There is thus obtained the corresponding dihydrochloride which, when recrystallized from hydrochloric acid, takes the form of white crystals.

Analysis Calculated Found C% 36.99 C% 36.69 36.78 11% 5.28 H% 5.23 5.25 N% 12.33 N%12.34 12.51

EXAMPLE 2 Preparation of 2,6-diamino-4-diethylaminophenol There is employed as starting material 2,6-dinitro-4- diethylaminophenol, which is reduced with a mixture of tin and hydrochloric acid. The desired product is thereafter liberated by passing a current of hydrogen sulphide over the chloro-stannate intermediate thus obtained.

Analysis Calculated Found C% 39.40 C% 39.38 39.74 H% 6.56 1-[% 6.27 6.51 N% 13.80 13.98 13.62

EXAMPLE 3 Preparation of 2,6-diamino-4-dimethylaminophenol trihydrochloride The procedure as indicated in Example 2 is followed, except that there is employed as starting material 2,6- dinitro-4-dimethylaminophenol instead of 2,6-dinitro- 4-diethylaminophenol.

EXAMPLE 4 tion, the dihydrochloride of 2,5-diamino-4- methoxyphenol.

Analysis Calculated Found C% 37.00 C% 36.79 37.38 H% 5.28 11% 5.23 5.39 N% 12.33 N% 12.13 11.97

EXAMPLE 5 Preparation of 4-N,N-diethylamino-2-aminophenol 4-N,N-diethylamino-2-aminophenol is prepared from 2-nitro-4-N,N-diethylamino anisole which is reduced by means of iron and acetic acid. The resulting product is then refluxed in a concentrated solution of hydrobromic acid. After cooling, the 4-N,N-diethy1amino-2- aminophenol crystallized in the form of its dihydrobromide.

Analysis Calculated Found N% 8.18 N% 8.05 8.22

EXAMPLE 6 A dyeing solution according to the invention is prepared by mixing:

6-amino-4-methoxy-2-aminophenol sulphate 2.5 g sodium carbonate, q.s. for pH 7 water q.s. for 100 cc This solution is applied to hair containing 90 percent of white hairs and left in contact therewith for to minutes. After washing and rinsing, a khaki coloration is obtained.

EXAMPLE 7 A dyeing solution according to the invention is prepared by mixing:

6-amino-4-methoxy-2-aminophenol sulphate 2.5 g N/l sodium carbonate, q.s. for pH 7 20% ammonia 5 cc water q.s. for 100 cc To the mixture thus prepared are added 8 cc of hydrogen peroxide (130 vol.). The solution obtained is applied to brown hair containing percent of white hairs. After 20 minutes, the hair is rinsed and then shampooed. A dark ash-blond coloration is obtained.

EXAMPLE 8 A dyeing solution according to the invention is prepared by mixing:

6-amino-4-diethylamino-Z-aminophenol trihydrochloride 3 g sodium hydroxide q.s. for pH 7 water q.s. for cc By applying this solution to hair containing 90 percent of white hairs and leaving it in contact therewith for 15 to 20 minutes and thereafter washing and rinsing it, a strong green coloration is imparted to the hair.

EXAMPLE 9 A dyeing solution according to the invention is prepared by mixing:

6-amino-4-diethylamino'2-aminophenol trihydrochloride 3 g N/l sodium hydroxide. q.s. for pH 7 4 CC 20% ammonia diethylenetriaminepentaacetic acid, sodium salt 0.5 g water, q.s. for 100 cc This solution, when mixed with 8 cc of hydrogen peroxide (100 vol.) and applied to brown hair containing 60 percent of white hairs, gives after a contact period of 25 minutes, rinsing and shampooing, a light brown coloration having green reflections.

EXAMPLE 10 A dyeing solution according to the invention is prepared by mixing:

5-amino-4-methoxy-2-aminophenol dihydrochloride 2 g sodium hydroxide, q.s. for pH 7 water q.s. for 100 cc By applying this solution to hair containing 90 percent of white hairs, and leaving it in contact therewith for 15 to 20 minutes and thereafter washing and rinsing it, the hair is given a strong violet coloration.

EXAMPLE 1 l A dyeing solution according to the invention is prepared by mixing:

5-amino-4-methoxy-2-aminophenol dihydrochloride 2 g N/l sodium hydroxide, q.s. for pH 7 20 ammonia 6 cc sodium bisulphite 2.5 g water q.s. for 100 cc With this solution are mixed 8 cc of hydrogen peroxide vol.) whereafter it is applied to light brown hair containing 60 percent of white hairs. After a contact period of 20 to 25 minutes, rinsing and shampooing a dark blond coloration tinged with violet-pink is obtained.

EXAMPLE 12 A dyeing solution according to the invention is prepared by mixing:

4-N,N-diethylamino-Z-aminophenol,

dihydrobromide 3 g sodium carbonate q.s. for pH 7 water q.s. for I cc By applying this solution to hair containing 90 percent of white hairs and leaving it in contact therewith for about 20 minutes, the hair is given a chestnut pink coloration, after washing and rinsing.

EXAMPLE 13 A dyeing solution according to the invention is prepared by mixing:

4-methoxy-2-aminophenol hydrochloride 0.15 g 6-amino-4-diethylamino-2-aminophenol trihydrochloride 0.15 g 4-methoxy-2-amino-(B -hydroxyethyl) aniline 0.8 g sodium carbonate, q.s. for pH 7 water q.s. for 100 cc This solution is applied to light brown hair containing 80 percent of white hairs. It is left in contact therewith for 20 minutes and after washing and rinsing the hair has a light gold-brown tint.

EXAMPLE 14 A dyeing solution according to the invention is prepared by mixing:

4-methoxy-2-aminophenol hydrochloride 0.15 g 6-amino-4-diethylamino-2-aminophenol trihydrochloride 0.15 g 4-methoxy-2-amino-( B hydroxyethyl) aniline 0.8 g N/l sodium hydroxide, q.s. for pH 7 20 ammonia cc water q.s. for 100 cc There are added to this solution atthe time of use 8 cc of hydrogen peroxide (130 vol.), whereafter it is applied to brown colored hair containing 80 percent of white hairs. After a contact period of 25 minutes, rinsing and shampooing, a light red-brown coloration is obtained.

EXAMPLE 15 A dyeing solution according to the invention is prepared by mixing:

4-methoxy-2-aminophenol hydrochloride 0.5 g 4-methoxy-2-amino-( B -hydroxyethyl) aniline 0.3 g 5-amino-4-methoxy-2-aminophenol dihydrochloride 0.2 g sodium carbonate, q.s. for pH 7 water q.s. for I00 cc By applying this solution to light brown hair containing 90 percent of white hairs and leaving it in contact therewith for 15 to minutes and thereafter washing and rinsing it, there is imparted to the hair thus treated a mauvish dark ash-blond coloration.

EXAMPLE 16 A solution according to the invention is prepared by adding to the solution described in Example 6, 5 cc of 20 percent ammonia and 8 cc of hydrogen peroxide (130 vol.).

By applying this solution in the same way as above to brown hair containing 50 percent of white hairs, a golden light brown coloration is obtained.

EXAMPLE 17 The following solution is prepared:

6-amino-4-methoxy-2-aminophenol sulphate 3 g 20 ammonia 7 cc water q.s. for 100 cc 50 cc of this solution are mixed with 50 cc of a hydrogen peroxide solution and applied to hair containing percent of white hairs. After 25 minutes of contact, the hair is shampooed, rinsed and dried.

It has a blond coloration.

EXAMPLE 18 The following solution is prepared:

5-amino-4-methoxy-2-aminophenol dihydrochloride 2.3 g

sodium carbonate q.s. for pH 7 20% ammonia 7 cc water q.s. for cc 50 cc of this solution are mixed with 50 cc of a hydrogen peroxide solution and applied to hair containing 90 percent of white hairs. After 25 minutes of contact, the hair is shampooed, rinsed and dried.

It has an ash blond tint with mauve glints.

EXAMPLE 19 The following solution is prepared:

6-amino-4-dimethyl-2-aminophenol dihydrochloride 3 g sodium carbonate q.s. for pH 7 20% ammonia 7 cc water q.s. for 100 cc 50 cc of this solution are mixed with 50 cc of a hydrogen peroxide solution and applied to hair containing 90 percent of white hairs. After 25 minutes of contact, the hair is washed, rinsed and dried.

It has a blond coloration.

EXAMPLE 20 The following solution is prepared:

4-meth I-S-hydroxy-Z-aminophenol percent of white hairs. After 25 minutes of contact, the hair is shampooed, rinsed and dried.

It has a deep brown violet tint.

EXAMPLE 21 The following solution is prepared:

4-methyl-S-hydroxy-2-methylaminophenol hydrochloride 0.5 g -amino-4-diethylamino-Z-aminophenol trihydrochloride 0.4 g 4-methoxy-2-amino-( B -hydroxyethylaniline) 0.1 g sodium carbonate q.s. for pH 7 water q.s. for 100 cc 50 cc of this solution are mixed with 50 cc ofa hydrogen peroxide solution and applied to hair containing 90 percent of white hairs. After 25 minutes of contact, the hair is shampooed, rinsed and dried.

it has a light golden brown tint.

EXAMPLE 22 The following solution is prepared:

2-chloro-5-amino-hydroquinone hydrochloride 0.5 g 6-amino-4-methoxy-2-aminophenol sulphate 0.5 g -methyl--amino-hydroquinone hydroc loride 0.1 g sodium carbonate q.s. for pH 7 water q.s. for 100 cc 50 cc of this solution are mixed with 50 cc of a hydrogen peroxide solution and applied to hair containing 90 percent of white hairs. After 25 minutes of contact, the hair is shampooed, rinsed and dried. It has a flat dark brown tint.

It is known that the prior art compound 6-methoxy- 2,4-diaminiphenol tends to lose its coloration when it is exposed to natural weathering conditions caused by exposure to the sun and water. In contrast our tests show that the 5-amino-4-methoxy-2-aminophenol compound of this invention produced a color that remained unexpectedly stable when exposed to natural weathering conditions.

Moreover, the compounds of this invention, have unexpectedly low toxicity. For example our tests indicate that epicutaneous tissue can tolerate 2.5 to 3 time the amount of the 6-amino-4-diethylamino-Z-aminophenol compound of this invention than the prior art 2- methylamino-4-aminophenol compound.

What is claimed is:

1. A hair dye composition comprising water and a coloring amount of a dye selected from the group consisting of 6-amino-4-methoxy-2-aminophenol, 5- amino-4-methoxy-2-aminophenol, 6-amino-4-dimethylamino-Z-aminophenol, 6-amino-4-diethylamino-2- aminophenol and 4-diethylamino-2-aminophenol, having a pH of 7-11.

2. The composition of claim 1, in which said dye is selected from the group consisting of 6-amino-4-dimethylamino-Z-aminophenol, 6-amino-4-diethylamino-2- aminophenol and 4-diethylamino-2-aminophenol.

3. The composition of claim 1, wherein said dye is 6- amino-4-methoxy-2-aminophenol.

4. The composition of claim 1, wherein said dye is 5- amino-4-methoxy-2-aminophenol.

5. The composition of claim 1, wherein said dye is 6- aminc-4-dimethylamino-2-aminophenol.

6. The composition of claim 1, wherein said dye is 6- amino-4-diethylamino-2-aminophenol.

7. The composition of claim 1, wherein said dye is 4-diethylamino-2-aminophenol.

8. The composition of claim 1, containing approximately 0.5 to 5 percent by weight of said dye.

9. The process of dyeing live human hair comprising applying thereto coloring amounts of the dyeing composition of claim 1.

' UNITED STATES PATENT QFFICE CERTIFICATE OF CORBECTIGN PatentNo', 3,738,799 Dated June 12 1973 Inventm-s) GREGOIRE KALOPISSIS and ANDREE EUGAUT I t'is certified that error appears in the above-identified patent and that said'Letters. Patent are hereby corrected as shown below:

[30] Foreign Apnlication Priority Data July 11, 1962 France, .PV 903,703

July 3.,' 1963- France. .PV 9 40 ,212

Signed and sealed this 27th day of November 1975.

(SEALI Attest: I

EDWARD MQFLETCHERJR'; RENE D. TEGTMEYER Attesting Officer Acting Commissioner of Patents P 9 0 {10-69) i t uscoMM-Dc scam-P69 u '1 oovzewagwr Penning OFFICE: 1969 6-in-1 

2. The composition of claim 1, in which said dye is selected from the group consisting of 6-amino-4-dimethylamino-2-aminophenol, 6-amino-4-diethylamino-2-aminophenol and 4-diethylamino-2-aminophenol.
 3. The composition of claim 1, wherein said dye is 6-amino-4-methoxy-2-aminophenol.
 4. The composition of claim 1, wherein said dye is 5-amino-4-methoxy-2-aminophenol.
 5. The composition of claim 1, wherein said dye is 6-amino-4-dimethylamino-2-aminophenol.
 6. The composition of claim 1, wherein said dye is 6-amino-4-diethylamino-2-aminophenol.
 7. The composition of claim 1, wherein said dye is 4-diethylamino-2-aminophenol.
 8. The composition of claim 1, containing approximately 0.5 to 5 percent by weight of said dye.
 9. The process of dyeing live human hair comprising applying thereto coloring amounts of the dyeing composition of claim
 1. 